Plant response agents



Patented May 5, 1953 PLANT RESPONSE AGENTS Nathaniel Tischler, Palmyra, N. J., assignor to Sharples Chemicals Inc., a corporation of Delaware No Drawinga Application June 13, 1951,

, Serial N0. 231,442

17 Claims. (Cl. lb-2.5)

1 This invention relates to new and improved compositions of matter which are'used for treating growing plants to alter the normal life cycle of said plants with advantageous results. It is particularly concerned with phytotoxic compositions which contain at least one of the 3,6-endoxohydro-orthophthalic acids as active ingredients, that is, as plant response agent.

Phytotoxic compositions containing at least one of the aforesaid acids, and particularly 3,6- endoxo 1,2,3,6 tetrahydro-orthophthalic acid and/or 3,6endoxohexahydro-orthophtha1ic acid, per' se or in equivalent form, and'more particularly the exo-cis isomers, are highly efiective for the purpose, and it is a feature of this invention to provide compositions containing the above active ingredients in admixture with simple, read,- ily available materials which enhance, or intensify the plant response activity of the above active ingredients. These and other features will become apparent to persons skilled in the art as the specification proceeds.

Co-pending application Serial No. 81,026, filed March 11, 1949, by Nathaniel Tischler and Ernest P. Bell, which has matured into Patent No. 2,576,080, granted November 20, 1951, teaches the efficacy of the 3,6-endoxohydro-orthophthali'c acids and their derivatives in bringing about useful plant response effects such as leaf abscission (partial or complete), blossom thinning, vinekill, total destruction of the plant, adventitious root formation, or delay of fruit drop, the particular plant response manifested depending to a large extent upon the applied concentration of the response agent, and the species and degree of maturity of the plant undergoing treatment.

The use of 3,6-endoxohexahydro-orthophthalic acid, per se or in equivalent form, for the above purposes is particularly described and claimed in the co-pending application of Ernest P. Bell and Nathaniel Tischler, Serial No. 131,501, filed December 6, 1949, now Patent No. 2,576,081, granted November 20, 1951; and the use of 3,6-endoxo- 1,2,3,6-tetrahydro-orthophthalic acid, per se or in equivalent form, for such purposes is particularly described and claimed in the co-pending application of the same inventors, Serial No. 131,502, filed December 6, 1949, now Patent No. 2,576,082, granted November 20, 1951. Both of these applications are continuations-in-part of said firstmentioned application.

The above-mentioned compounds asapplied to plants may be in the form of the acid per se or in other form, such as in the form of the anhydride and/or a salt which contains the corresponding anion or anions. of ortho configuration, the same as in the case of the acid per se, said anion or anions being either acid or neutral in character, in chemical combination with a sufficiency of cation or cations to satisfy valence requirements, such as one or more metal and/or metalloid cations such as sodium, potassium, calcium, strontium, magnesium, aluminum, iron, cobalt, nickel, zinc, cadmium mercury, copper, ammonium, mono-, diand trialkylammonium, mono-, diand trialkanolammonium, and mixed alkylalkanolammonium which is N-substituted by from 2 to 3 radicals of the type indicated.

Thus the acid is the active material, and this is true whether it is used as such, or in the form of a salt, or anhydride, or other equivalent form. These changes at the carboxyl groups are mere changes in form rather than changes in substance.

Turning now to the present invention, which for convenience will be described more particularly with reference to 3,6-endoxohexahydroorthophthalic acid and 3,6-endoxo-1,2,3,6-tetrahydro-orthophthalic acid (per se or in equivalent form) as active plant response ingredients of my new compositions, it is pointed out that said acids are appreciably soluble in Water. The other forms are also water-soluble. Some of them are highly soluble, while others have a lesser degree of solubility. However, it is preferred to employ compounds having a solubility in water to the extent of at least 0.1% by weight, and still more particularly of at least 1% by weight.

Water solubility is desirable so that anions (acid or neutral or both) are formed when the acids, per se or in chemically equivalent form, are dissolved in water. The desirability of such anions will presently become apparent.

Acid anions may be theoretically illustrated by reference to the acid 3,6-endoxohexahydroorthophthalate anion, by which is meant a univalent anion having a structure defined by the formula wherein X is a cation, considered by modern theory'to be hydrogen.

Neutral anions may be theoretically illustrated by reference to the'neutral 3,6-endoxohexahydroorthophthalate anion by which is meant a divalent anion having a structure defined by the Thus the foregoing active ingredients may be defined as compounds which when in the presence of water yield anions having thesconfiguration in which Y represents one'ofthegroupponsist ing of an unsatisfied valenceand' a cation; and in which R represents'one of the'group'consi'sting of the vinylene radical and the ethylene radical.

Although the present applicant does not Wish to be bound by any particular theory as to the mechanism "whereby useful plant response effects are produced, a considerable amount of experimentation strongly indicates 'that'said' effects are brought about'bythe'existence in aqueous media of anion or'anions' (acid and/or neutral) of the type illustrated above; Both neutral anion and acid. anion are effective. A salient'feature'of this theory is that the acid or acids'of the invention, when applied per se, or in equivalent form, to a living plant, makes the desired anion or anions (acid and/or neutral) available-to the'plant, at or near the site of application, and through translocation phenomena, at points far removed from the site of application.

The desired anion oranions are made available by virtue of the fact that the acids per 'se, and their equivalent forms, are water-soluble and ionizable. absorbed into the vascular system ofa plant, it dissolves in the aqueous plant juices and provides the functioning anion or anions. The resulting physiological activity is believed to be ascribable to the presence. of said anion or anions. The acids per se and their equivalent forms may thus be regarded as very convenient. media for furnishing the desired anion or anions to susceptible portions of the plant.

It follows, therefore, that. the acids per se and their equivalent forms are equally usable.

The foregoing compounds are highly effective for the intended purpose.

I have discovered that the amount of the re spective compounds used to produce a given plant response effect may be markedly reduced, or the plant response efiect obtained with a given amount of active ingredient markedly increased, by admixing with any said compound or compounds, one or more of the group consisting of diglycolic acid and the ammonium and substituted ammonium salts of said acid; said salts being either in neutral or acid form. Particular substituted ammonium salts are the alkylammonium salts, alkanolammonium salts, and mixed alkylalkanolammonium' salts.

Examples of salts of diglycolic-acidaare ammonium diglycolate and ammonium acid I diglycolate; mono-, di-, and tri-alkylammonium salts having from. 1 .to 4 carbon. atoms in'eachal- Therefore, when. such a compound is kyl radical; mono-, diand trialkanolammonium salts having from 2 to 3 carbon atoms in each alkanol radical; and mixed alkylalkanolammonium salts which are N-substituted by from 2 to 3 radicals of the type and carbon content indicated. The substituted ammonium salts include both neutral: and acid salts, wholly analogous to the ammonium salts mentioned above.

In the case of salts containing more than one ammonium and/or substituted ammonium radicals. (i. e., cations), said cations may be the same or different.

The, preparation. of the salts falling within the scope. of the invention may be accomplished by any means known to the art, such as by neutralization of the acid with the requisite amount of theselected base or mixture of bases. In general, water is an excellent liquid medium for carrying out such neutralizations, although at times the use of other media may be desirable.

Likewise, the preparation of the. 3,6-endoxohydroorthophthalic acids, per se and in. equivalent form, may be accomplished by any means known toythe art, and suitable methods will suggest themselves to persons skilled in chemical synthesis upon becoming familiar with the chemical structure of such compounds.

The amount of additive or intensifier to be admixed with the endoxo compounds may vary over a very wide range, and even a small amount of the intensifier will produce a useful synergistic intensifying effect. Generally speaking, for practicable purposes, proportions of intensifier to active ingredient'of from 1:10 to 50:1, and particularly from 1:1 to 20:1, are very useful.

The. intensifier and the. active ingredient may be-admixedin any, desired manner: such as by mere mechanical mixing in solid form, or while in solution-in a common solvent such as water. In the latter case the solution maybe marketed as such, or if desired, may be dried, such as by spray or drum drying. In any case, it is preferred to have a solid admixture in .finely divided form and sufficiently dry to be free flowing.

The admixtures are applied to the crop or plants in any desired manner, such as in the form of a solid, for example, by dusting, or in the form of a liquid, for example, by spraying.

Compositions may be formulated by mixing the admixture. containing the intensifier and active ingredient with any desired liquid or solid carriers, such as any of the finely divided solid carriers known in the dustingart, which are preferably of large surface. area, such as clay, for example, fullersv earth, pyrophyllite, talc, bentonite, kieselguhr, diatomaceous earth, etc. Any of the commercial clays available on the market in finely divided form may be used, and particularly those which are normally employed as insecticide carriers. Commercial clays, it will be understood, are generally identified by trade names (reflecting the source and mode of processing), of which Homer Clay, Celite, and Tripoli may be mentioned as typical.

Non-clay carriers which may be formulated with my admixture include, for example, sulfur, volcanic ash, calcium carbonate, lime, Icy-product lignin, lignocellulose, flour, such as-Wood, walnut shell, Wheat, soybean, potato, cottonseed, etc.

Any desired mixture may be prepared by any suitable method. Thus, if a solid, the active ingredient may be ground to a fine powder and tumbled together with the intensifier, or the in- .tensifier and the active ingredient may be ground together; alternatively, the active ingredient'in liquid form, including solutions, dispersions, emulsions, and suspensions thereof, may be admixed with the intensifier in finely divided form in amounts small enough to preserve the freeflowing property of the final dust composition. Or excess liquid may be removed, such as by vaporization, for example, under reduced pressure. The same applies to mixtures of the active ingredient, the intensifier, and any finely divided solid carrier and/or other material.

When solid compositions are employed, in order to obtain a high degree of plant coverage with minimum poundage per acre, it is desirable that the composition be in finely divided form. Preferably, the dust containing the active ingredient should be sufficiently fine that substantially all will pass through a 50 mesh sieve, and more particularly through a 200 mesh sieve. Excellent results have been obtained in which the dust composition is comprised predominantly of particles in the range from to 45 microns. Finer dusts, such as those consisting largely of particles in the range of 5 microns and below have excellent covering capacity but are somewhat more subject to drift and are more expensive to prepare.

For spray application the admixture may be dissolved or dispersed in a liquid carrier such as water or other suitable liquid.

Aqueous solutions or dispersions are economical and desirable. In general, the choice of the particular liquid carrier employed will be guided somewhat by prevailing circumstances, such as its availability, its solubility or dispersion characteristics toward the particular admixture employed, and/or its toxicity toward the plants undergoing treatment. In general, water is an excellent liquid carrier.

Thus, spray formulations comprising the active ingredient in the form of a solution, suspension, dispersion, or emulsion, in aqueous or non-aqueous media may be employed.

Emulsions or dispersions of the admixture in the liquid carrier may be prepared by agitation of the admixture with the carrier. This is commonly done at the time of spraying. Preferably, however, the agitation should take place in the presence of an emulsifying or dispersing agent (surface-active agent) in order to facilitate the preparation of said emulsion or dispersion. Emulsifying and dispersing agents are wellknown in the art, and include, for example, fatty alcohol sulfates, such as sodium lauryl sulfate, aliphatic or aromatic sulfonates, such as sulfonated castor oil or the various alkaryl sulfonates (such as the sodium salt of monosulfonated nonyl naphthalene or tertiary dodecyl benzene), and non-ionic types of emulsifying and dispersing agents such as the high molecular weight alkyl polyglycolethers or analogous thioethers such as the decyl, dodecyl and tetradecyl polyglycolethers and thioethers containing from to '75 carbon atoms.

The use, if desired, of adjuvants, such as Wetting agents and/or humectants (water-retaining agents), is also contemplated in connection with solutions of the admixture, such as water solutions. Any suitable wetting agent and/or humectant may be employed for this purpose, such as the wetting agents more particularly referred to above. Examples of humectants are glycerine, diethylene glycol, ethylene glycol/polyethylene glycols generally, and water-soluble su'garsand sugar containing mixtures, such as glucose, fructose, galactose, mannose, arabinose, xylos'e', su-

orose, maltose, lactose, raifinose, trehalose, dextrins such as white dextrin, canary dextrin, Brit,- ish gum, etc., honey, molasses, maple syrup, maple sugar, and starch syrups such as corn syrup, etc.

For adjuvant purposes, any desired quantity of wetting agent may be employed, such as up to 250% or more based on active ingredient. For Wetting purposes, the amount of adjuvant used may be considered to be that required to impart the desired wetting qualities to the spray solution as formulated, such as approximately 0.05% by weight of the spray solution. The use of considerably larger amounts is not based upon wetting properties, although present, but is a function of the physiological behavior of the wet ting agent after spraying upon the plant.

It should be considered that once the solution has been sprayed upon the plant, the concentration of wetting agent existing upon the plant is in no sense a function of the concentration existing in the original spray solution. Thus, evaporation might concentrate the wetting agent considerably, or the presence of dew on the plant surfaces, or of plant juices on the plant surfaces might considerably dilute this agent.

It will, of course, be understood that wetting agents, particularly in solid form, may be compounded with the admixture when in solid form.

Although the admixture of active ingredient and intensifier may be applied to the growing plant in concentrated form, it is usually desirable to employ liquid or solid formulations, for example, as discussed above, in which the active ingredient constitutes less than 30% by weight of the total, such as less than 10% and even as low as 0.1%.

Other substances than the carrier, surface active agent, and/or humectant may be included in solid or liquid formulations if desired. Thus, active ingredients other than those disclosed herein and compatible with the admixture may be added if desired for any particular purpose. Also substances may be added to bring about various physical improvements such as the prevention of lumping during storage, or improvement with respect to coverage, moisture adsorption, adherence, etc. Such other active ingredients may be included in said formulations to accomplish various physiological effects. For example, it may at'times be expedient to include singly or in combination, substances such as fungicides, insecticides, bactericides, or types of plant response agents other than those agents discussed herein.

In practice of the process as applied to defoliation, the rate of application (i. e. the amount of admixture per crop unit) for best results will depend among other factors upon the species of plants bein treated and upon their maturity. In any event, the amount of active ingredient employed for the same plant response effect will be substantially lower than when the intensifier is not present.

As a rule the more mature the plant at the time of application, the less active material is required. In practice, the crop is normally treated for defoliation purposes, 1 or 2 weeks prior to harvesting. In some instances, more than one application may be desirable, especially if heavy rains or winds should occur soon after the application, or to obtain an accumulative efiect. Then too, in order to avoid possible injury to any particular crop, it may be desirable for an inexperienced operator to apply the deof my intensifier.

foliant initially at a relatively low rate, and to follow with a second application if necessary after observation of the first effects, to obtain the degree of defoliation desired.

Use of dosages greatly in excess of the minimum required for good defoliation may result in shock to the plant with attendant injury to the remainder of the plant.

In fact, the plant response compositions of the present invention are effective herbicides when used in amounts substantially greater than those required for defoliation, and they may be used advantageously for the killing of plants or vines (as in the case of potatoes) when desired, such as, for the killing of undesired plants, for example, weeds or grasses, or for the killing of crops, irrespective of whether such undesired plants or crops are of species which lend themselves to defoliation.

Thus when defoliation is the objective the quantity applied should be sufiicient to cause at least the major portion of the leaves to dry up and/or to drop from the living plant, but insufiicient to cause substantial herbicidal action on the plant. On the other hand, when plant killing is the objective, any amount sumcient for this purpose may be applied. In the latter connection, since diiierent species of plants vary markedly in their relative resistance to heribicidal action, selective killin of plant species may be practiced. Such selectivity may be varied by compounding, such as with adjuvants, for example, wetting agents, in .addition to the use of an intensifier.

I am aware of the fact that it has been proposed to use certain ammonium salts, such as ammonium sulfate, in combination with phenolic substances, such as dinitroalkylphenols and pentachlorophenol, for plant response purposes. The purpose of such use of ammonium salts as explained by Crafts and Reiber, Hilgardia, volume '16, pages 487-499, and by Crafts, :Science, volume 108, pages 85-86, is to make available the free phenol at the plant surface from an aqueous solution of a Water-soluble salt of said phenol. The phenol in such cases is the active plant response substance and is continuously regenerated at the plant surface from its water-soluble salt by virtue of the presence of the ammonium salt.

As the free phenol is adsorbed by the plant sur- L face, further free phenol is generated under equilibrium conditions. The plant response effect of the free phenol is not enhanced or intensified by such procedure, or in "other words,

is substantially the same as that obtained by I the application directly to the plant of a similar quantity of free phenol. In view of the insolubility of the phenol 'in water, this procedure is adopted .in order to make available the use .of water as a vehicle for applying the plant response agent,'i. e. herbicide, to the plant surfaces.

In the case of my invention, on theother hand, the plant response efiect obtained from a given quantity of active ingredient is greater than that obtained by the Japplicationof ,thesamequantity of "the particular active ingredient to the plant in the absence of my intensifier. vIn fact, the

plant response efiect obtained with the same quantity of active ingredient may be increased many times by the addition of larger quantities .The intensification begins to manifest .itself by the sadditionof :a .small proportion-of my intensifier andiincreases-to agpoint of optimum intensification .by :the addition :of *in .creasingproportions.oiintensifier. :Forpptimum plant response effects, the proportion of intensifier to active ingredient may vary somewhat between specific active ingredients and between specific varieties of plants undergoing treatment, so that the exact proportion for optimum effect under all conditions cannot be given. However, the intensification of the plant response effect is present when a small quantity of intensifier is added, and the addition of intensifier beyond the point at which no further marked increase in intensification is obtained does no harm.

The exact mechanism by which the intensification of the above ingredient is obtained in the practice of my invention is not known. However. such intensification is cogently demonstrated by the following example which is by way of illustration and not or limitation.

EXAMPLE Three series of aqueous solutions of disodium 3,6-endoxohexahydroorthophthalate were prepared, each series consisting of four solutions having the following respective concentrations of this active ingredient: 0.00125 0.0025%, 0.005% and 0.0075%.

One series of solutions contained no intensifier. Each of the other two series contained, in addition to the active ingredient, a constant amount (0.05%) of an intensifier. The intensifiers employed in preparing the respective series of solutions were ammonium acid diglycolate and ammonium diglycolate. Thus the ratio of intensifier to active ingredient ranged from 6.6:1 to 40:1.

Separate groups of eight potted Dwarf Horticultural bean plants at the stage at which the first trifoliate leaf was still furled were dipped to the first nodes into the respective test solutions of each series, and excess solution was shaken oif. Approximately 2 ml. of solution remained on each plant. Thus the dosages of active ingredient per plant, depending on the respective concentrations of the test solutions, were approximately 25, 50, 100, and micrograms, respectively. The dosage of intensifier was constant, amounting to approximately 1000 micrograms.

One group of eight plants was not treated with any solution and was kept as a control.

Control tests using the intensifiers in the absence of active ingredient were also conducted. Groups of eight plants were treated with 0.05% aqueous solutions of the respective intensifiers, using the above-described method of application.

All plants used for this test were of the same age and had been grown at the same time and under the same conditions. After the test was commenced, treated plants and untreated controls were again kept under the same conditions and therefore were subjected to comparable growing conditions.

Observations were made 5 days after treatment, with results as summarized in the table. Several symbols are employed in this table, their meanings being as follows:

jltzlightly mod=moderately sev=severely bn burned .ret=retarded adh=adhering C=untreated control ;PL=primary leaves TS=trifoliate-shoots .23, for example, .meansleach of two plants'hada single primary leaf abscised; 3B, for example,

9 j means each of three plants had both primary leaves abscised.

TABLE I um, monononylammonium, monodecylammonium, monoundecylammonium, monododecylam- Physiological efiects Active ingredient per plant Intcnsifier micrograms 50 micrograms 100 micrograms 150 micrograms None PLltbn;TSas O. PLltbn;TS-as C. PLItbn;TS-ltret. 2ft); 9%); PLgmod 11; mo ret. Ammonium acid diglycolatcn PL-lt bn; TS-lt 1S; adh PLmod 3B, 28; adh PL- 3B, 3S; adh PL-sev I ret. bn; TS-lt ret. mod bn; TSmod bn; TS-sev ret.

r Ammonium diglycolate PL-lt bu; TS-lt 2S; adh PL-mod 1B, 45; adh Plr- 4B,4S;adh PL-sev ret, bn; TS-lt ret. mod dbl? TS- bn; TS-sev ret.

mo re Those plants which were not treated and those plants which were treated only with the intensifiers were entirely unaffected.

The endoxo compounds are theoretically capable of existing in three separate and distinct geometrically isomeric forms, namely, the exo-cis isomer, the endo-cis isomer, and the trans isomer, as defined in the case of the hexahydro compounds by Woodward and Baer, Journal of the American Chemical Society, '70, 1161-1166. Of these three isomers the exo-cis isomer is preferred in view of its outstandingly greater activity. Furthermore. the exo-cis isomer can be prepared more economically and conveniently. The endoxo ingredient in the foregoing examples was of the exo-cis isomeric form.

When the endoxo ingredients are used in the form of the acids per se and/or their anhydrides, aqueous solutions containing such acids and/or anhydrides probably contain non-ionized acid and/or anhydride in equilibrium with ionized material. Similar considerations might apply to some of the salts.

The alkylammonium salts of 3,6-endoxohydroorthophthalic acids, such as monoalkylamrnonium, dialkylammonium, or trialkylammonium salts preferably have from 1 to 12 carbon atoms in each alkyl radical, the totality of carbon atoms preferably being not more than 12. The alkanolammonium salts such as monoalkanolammonium, dialkanolammonium, or trialkanolammonium preferably have from 2 to 3 carbon atoms in each alkanol radical. The mixed alkylalkanolammonium salts such as monoalkyl monoalkanolammonium, dialkyl monoalkanolammonium, or monoalkyl dialkanolammonium preferably have from 1 to 4 carbon atoms in each alkyl radical and from 2 to 3 carbon atoms in each alkanol radical.

The neutral and acid alkylammonium salts of diglycolic acid such as monoalkylammonium, dialkylammonium, or trialkylammonium salts, preferably have from 1 to 4 carbon atoms in each alkyl radical. The alkanolammonium salts such as monoalkanolammonium, dialkanolammonium, or trialkanolammonium preferably have from 2 to 3 carbon atoms in each alkanol radical. The mixed alkylalkanolammonium salts such as monoalkyl monoalkanolammonium, dialkyl monoalkanolammonium, or monoalkyl dialkanolammonium preferablylhave from 1 to 4 carbon atoms in each alkyl radical and from 2 to 3 carbon atoms in each alkanol radical.

The following examples apply to both the active ingredient and the intensifier.

Examples of monoalkylammonium salts are the monomethylammonium, monoethylammonium, monopropylammonium, monobutylammonium, monoamylammonium, monohexylammoni um, monoheptylammonium, monooctylammonimonium and similar monoalkylammom'um salts of such acids.

Examples of dialkylammonium salts are the dimethylammonium, diethylammonium, dipropylammonium, dibutylammonium, diamylammonium, dihexylammonium, methylethylammonium, ethylpropylammonium, propylbutylammonium, butylamylammonium, amylhexylammonium, methylundecylammonium, and similar dialkylammonium salts of such acids.

Examples of trialkylammonium salts are the trimethylammomum, triethylammonium, tripropylammonium, tributylammonium, methyldieth- 'ylammonium, ethyldipropylammonium, propyldibutylammonium, methyldiamylammonium, ethyldiamylammonium, methylethylpropylammonium, ethylpropylbutylammonium, and similar salts of such acids.

Examples of monoalkanolammonium salts are the monoethanolammonium, monopropanolammonium, and similar salts of such acids.

Examples of dialkanolammonium salts are the diethanolammonium, dipropanolammonium, ethanoilpropanolammonium and similar salts of such ac1 s.

Examples of trialkanolammonium salts are the triethanolammonium, tripropanolammonium, ethanoldipropanolammonium, propanoldiethanolammonium and similar salts of such acids.

Examples of monoalkyl monoalkanolammonium salts are the methylethanolammonium, ethylethanolammonium, propylethanolammonium, butylethanolammonium, methylpropanolammonium, ethylpropanolammonium, propylpropanolammonium, butylpropanolammonium, and similar salts of such acids.

Examples of dialkyl monoalkanolammonium salts are the dimethylethanolammonium, diethylethanolammonium, dipropylethanolammonium, dibutylethanolammonium, dimethylpropanolammonium, diethylpropanolammom'um, dipropylpropanolammonium, dibutylpropanolammonium, methylethylethanolammonium, methylethylpropanolammonium, ethylpropylethanolammonium, ethylpropylpropanolammonium, propylbutylethanolammonium, propylbutylpropanolammonium, and similar salts of such acids.

Examples of monoalkyl dialkanolammonium salts are the methyldiethanolammom'um, ethyldiethanolammonium, propyldiethanolammonium, butyldiethanolammonium, methyldipropanolammonium, ethyldipropanolammonium, propyldipropanolammonium, butyldipropanolammonium, methylethanolpropanolammonium, ethylethanolpropanolammonium, propylethanolprooanolammonium, butylethanolpropanolammo ium and similar salts of such acids. As pointed out above the salts contemplated include both the acid salts and the neutral salts,

etergeas 11 and mixed salts, that is salts in which the cations are different.

The term plant as used herein is understood to include all portions of the plant, such as the roots, stems, leaves, blossoms, seeds, and fruits.

Among the plants which defoliate naturally and which may be defoliated by the use of this invention, are for example, cotton, potatoes, tomatoes, and beans such as soybeans and lima beans.

Examples of noxious weeds against which my compositions may be used for herbicidal effects are bindweed, chickweed, cocklebur, mares tail, shepherds-purse, broad-leaved plantain, Wild lettuce, ragweed, spurge, dock, and wild carrot.

My new compositions are generally applicable as herbicides, such as in pre-efnergence or preplanting practices for the control of weeds, in post-emergence treatment for control of weeds as to such useful crops to which the formulation evidences only slight or no herbicidal action, and otherwise following agricultural practices.

From the foregoing it can be seen that the endoxo compounds used in the practice of this invention, whether used as the acid or in equivalent form, are highly effective in regulating the growth characteristics of viable or living plants, and particularly of plants having vascular systems, when used in admixture with my intensifier. For example, the admixture may be employed to hasten defoliation of plants which defoliate naturally, or may be employed to terminate the life cycle of plants, or may be employed to retard the growing of seeds, or may be employed to selectively stunt or terminate the growth of certain unwanted plants to facilitate and favor the growth of wanted plants, or may be employed to terminate the growth of vines in favor of, or to facilitate harvesting of, the fruits of such vines, or may be employed to stimulate root growth on cuttings, etc. Other applications of the invention in the regulation of the growth characteristics of plants will occur to persons skilled in the art upon becoming familiar herewith.

Accordingly, it is to be understood that the particular description is by way of illustration and that the patent is intended to cover by suitable expression in the claims whatever features of patentabl novelty reside in the invention.

I claim:

1. A composition prepared for use as a plant response agent which comprises a compound selected from the group consisting of diglycolic acid and the salts of said acid with at least one of the group consisting of ammonia, alkyl amines, alkanol amines and mixed alkylalkanol amines; and a compound which when in the presence of water yields anions having the configuration in which Y represents one of the group consisting of an unsatisfied valence and a cation, and in which R represents one of the group consisting of the vinylene radical and the ethylene radical.

2. A composition prepared for use as a plant response agent comprising a compound which when in the presence of water yields anions of '3,6-endoxohexahydro-orthophthalic acid; and as an intensifier therefor a compound selected from Y the group consisting of diglycolic acid and the salts of said acid with at least one of the group 12 consisting of ammonia, alkyi amines, alkanol amines and mixed alkylalkanol amines.

3. The composition of claim 2 in which the anions are of the exo-cis isomeric form.

l. The composition of claim 3 in which the intensifier is ammonium diglycolate.

5. The composition of claim 3 in which the intensifier is ammonium acid diglycolate.

6. The composition of claim 3 in which the in tensifier is diglycolic acid.

7. The composition of claim 1 having admixed therewith a wetting agent.

8. The composition of claim 1 having admixed therewith a humectant.

9. A composition prepared for use as a plant response agent comprising a compound which when in the presence of water yields anions of 3,6 endoxo 1,2,3,6 tetrahydro orthophthalic acid; and as an intensifier therefor a compound selected from the group consisting of diglycolic acid and the salts of said acid with at least one of the group consisting of ammonia, alkyl amines, alkanol amines and mixed alkylalkanol amines.

10. The composition of claim 9 in which the anions are of the exo-cis isomeric form.

11. The composition of claim 10 in which the intensifier is ammonium diglycolate.

12. The composition of claim 10 in which the intensifier is ammonium acid diglycolate.

13. A method for regulating the growth characteristics of a plant, comprising applying to said plant a plant response composition comprising a compound selected from the group consisting of diglycolic acid and the salts of said acid with at least one of the group consisting of ammonia, alkyl amines, alkanol amines and mixed alkylalkanol amines; and a compound which when in the presence of water yields anions having the configuration s i I al a R o 1 in which Y represents one of the group consisting of an unsatisfied valence and a cation, and in which R represents one of the group consisting of the vinylene radical and the ethylene radical.

14. A method for inducing plant response in a living plant, comprising applying to said plant a composition comprising a compound which when in the presence of Water yields anions of 3,6-endoxohexahydro-orthophthalic acid, and a compound selected from the group consisting of diglycolic acid and the salts of said acid with at least one of the group consisting of ammonia, alkyl amines, alkanol amines and mixed alkylalkanol amines.

15. The method of claim 14 in which the anions are of the exo-cis isomeric form.

16. A method for inducing plant response in a living plant, comprising applying to said plant a composition comprising a compound which when in the presence of water yields anions of 3,6- endoxo 1,2,3,6 tetrahydro orthophthalic acid, and a compound selected from the group consisting of diglycolic acid and the salts of said acid with at least one of the group consisting of ammonia, alkyl amines, alkanol amines and mixed alkylalkanol amines.

1'7. The method of claim 16 in which the anions are of the exo-cis isomeric form.

NATHANIEL 'TISCHLER. No references cited. 

1. A COMPOSITION PREPARED FOR USE AS A PLANT RESPONSE AGENT WHICH COMPRISES A COMPOUND SELECTED FROM THE GROUP CONSISTING OF DIGLYCOLIC ACID AND THE SALTS OF SAID ACIDS WITH AT LEAST ONE OF THE GROUP CONSISTING OF AMMONIA, ALKYL AMINES, ALKANOL AMINES AND MIXED ALKYLALKANOL AMINES; AND A COMPOUND WHICH WHEN IN THE PRESENCE OF WATER YIELDS ANIONS HAVING THE CONFIGURATION 